An asphaltic composition

ABSTRACT

Asphaltic compositions are prepared having suitable softening points, needle penetration and stain values for use in paper laminates. These compositions are prepared by airblowing a blend of a major amount of asphalt and a minor amount of foots oil derived from slack wax from a medium lubricating oil distillate.

United States Patent Fauber 51 May 16, 1972 [54] ASPHALTIC COMPOSITION[72] Inventor: Eugene M. Fauber, 6941 Stateline Avenue, Hammond, Ind.46324 [22] Filed: Nov. 4, 1970 I21] Appl, No; 86,974

Related US. Application Data [63] Continuation-impart of Ser. No.727,075, May 6,

1968, abandoned.

[52] US. Cl ..l06/279, 208/18, 208/22, 208/39 [51] Int. Cl ..C08h 13/00,C08h 17/22, C08i 1/46 [58] Field of Search ..106/273-285, 270-271,106/311; 208/3, 4, 6,11,18, 23, 44, 39, 21, 40

[56] References Cited UNITED STATES PATENTS 2,069,927 2/1937 Rhodes eta1. 106/278 X Primary Examiner.loan B. Evans Attorney-Thomas J Cloughand Robert J. Mawhinney [5 7] ABSTRACT Asphaltic compositions areprepared having suitable softening points, needle penetration and stainvalues for use in paper laminates. These compositions are prepared byairblowing a blend of a major amount of asphalt and a minor amount offoots oil derived from slack wax from a medium lubricating oildistillate.

8 Claims, No Drawings ASPHALTIC COMPOSITION This application is acontinuation-in-part of application Ser. No. 727,075, now abandoned.

This invention relates to novel asphaltic compositions comprisingasphalt-foots oil combinations suitable, for example, for use as paperlaminates. More specifically, this invention relates to blends ofasphalt and foots oil which are suitable for use in making paperlaminates and which are produced by airblowing a blend of asphalt and afoots oil fraction from the production of paraffin wax.

in order to be useful for making paper laminates it is necessary thatasphalts employed have acceptable softening point (e.g. about l852l5 F.,R&B), needle penetration (e.g. about 20-50 at 77 F.) and stain testvalues (e.g. Barber Stain Value in the range from 1 to 2, preferably 1).If the asphalt has too low a softening point, it has a tendency to flowat elevated temperatures thus permitting lateral movement of thelaminated paper sheets with respect to one another. If the needlepenetration is too low, the laminate lacks flexibility. High stainvalues (e.g. Barber Stain Value greater than 2) result in an unsightlyproduct. Inasmuch as the asphaltic residues from crude oil may notpossess acceptable properties, some sort of treatment is often requiredbefore the asphalt can be used to make laminates. It is known that theproperties of asphaltic residues may be altered by air oxidation,specifically by airblowing. However, many of these asphaltic residues,when airblown to a satisfactory softening point to be used in preparinglaminates,'are then found to have too low a penetration or too high astain value to be satisfactory.

It is well known that if an asphaltic material airblows to give too lowa penetration for a desired softening point, petroleum gas oils ofvarious types can be added to the asphalt before airblowing to causehigher, and in some cases much higher, penetration for a given softeningpoint than would have been obtained by airblowing the asphalt alone.However, petroleum gas oil, while permitting a higher penetration whenthe asphalt is air blown to the desired softening point, also causeundesirably high stain test values (e. g., Barber Stain Values greaterthan 2).

It is, therefore, an object of the present invention to prepare anasphaltic composition suitable for use in preparing paper laminates.More specifically, it is an object of this invention to provide anasphalt composition which can be airblown to give a product havingsatisfactory needle penetration, softening point and stain test valuesto be used in the preparation of laminates constructed, for example,from kraft paper or corrugated paper or board.

These and other objects of the present invention are accomplished by anasphaltic composition which comprises an airblown mixture of a majoramount (i.e. greater than 50 percent by weight) of asphalt and a minoramount, often about 0.5 percent to about 20 percent by weight,preferably about 2.5 percent to about percent by weight based on thetotal asphaltic composition, of a first pass foots oil fraction obtainedfrom medium slack wax. The composition is airblown to the desiredsoftening point. It has been found that the resulting airblown product,unlike unmodified asphalts, also gives satisfactory penetration andstain test values.

The foots oil of this invention is a by-product in the production ofparaffin wax and is the first foots oil fraction obtained from slack waxderived from a medium lubricating oil distilled from a mineral oil. Thefoots oil can be prepared in the following manner. A waxy petroleumcrude oil is fed to a crude still and various cuts are taken offincluding a cut called medium lube distillate which is the primarysource of the foots oil used in this invention and which boils primarilyin the range of about 700-l ,000 F., preferably about 800-900 F and hasan A.P.l. specific gravity of about 26, e.g. about 25.5 to 26.5. Thismedium lube distillate may advantageously be further refined to improvecolor stability by solvent extraction using, for example, phenol orfurfural to remove aromatic type compounds. The lube distillate or theraffinate from solvent extraction is further refined by dewaxing, oftenat relatively low temperatures of, for example, about -l0 F usingvarious solvents or mixtures of solvents such as methyl ethyl ketone,benzene, acetone, and toluene to produce, after removal of the solvent,what is called a base lube oil stock and a slack wax. The slack wax isfurther refined to produce a deoiled slack wax and a foots oil, forinstance, by further solvent extraction, using the same solvents but athigher temperatures, e.g. about 45 F as in the dewaxing step above or bysweating.

The foots oil of this invention is relatively low in aromatic compoundsand is composed principally of n-paraffins, isoparafilns and monocyclicnaphthenes. More specifically, the composition of the foots oil of thisinvention is typically, by weight, about 40-50 percent n-paraffins,about 5-15 percent iso-paraffins, about 35-45 percent monocyclicnaphthenes and about 1-5 percent aromatics. The properties andcomposition of a typical foots oil composition, made by the processdescribed, are shown in Tables I and II respectively.

TABLE I Properties of lst foots oil from medium slack wax TABLE IIComposition by Mass Spectrometer Analysis Carbon no. distributioniso-Paraffins monocyclic- Naphthenes aromatics Asphalts which may bealtered by the addition of the foots oil of this invention to havesuitable airblowing characteristics to be used as laminating asphaltsare asphaltic residues from mineral crude oils. These asphalts have aneedle penetration (ASTM-DS) at 77 F. in the range of about to 300, andoften have softening points of about 95-l 10 F.

Air-blowing of the foots oil-asphalt composition of this invention canbe carried out at temperatures of about 400 to 600 F often about 450 to550 F. for a period of time sufficient to give a softening point ofabout to 220 F., preferably about 208-2l2 F., and a needle penetrationof about 20 to 50, preferably about 20-25 at 77 F. For example,airblowing can be carried out at a temperature of 500 F. with 3.3 cu.ft. of air per hour per lb. of foots oil-asphalt charge. Airblown footsoil-asphalt composition of this invention can be produced to meetlaminating asphalt specifications of at least about 20, e.g. -25penetration at 77 F., 208-212 F. softening point (R&B), and Barber StainValue in the: range of 1 to 2, preferably 1. Compositions prepared bythe process of this invention were tested using ASTM-D36, StandardMethod of Test for Softening Point of Bituminous Materials, Ring andBall Method, and ASTM-DS, Standard Method of Test for Penetration ofBituminous Materials.

Stain values were obtained using the Barber Stain Test. in the BarberStain Test i gram of the bituminous material is weighed to the nearest0.05 gram and placed between two pads of cigarette papers, eachcontaining 12 3 X 4 inch sheets. The papers are placed in an over at 130F. for 120 hours under a 3 oz. tin filled with shot weighing 400 grams.The stain value is the number of stained sheets below and above thesample divided by two, counting the sheet next to the sample as one. Thecigarette paper used in the comparative tests was No. 4 Washingtongrade.

Compositions were formulated as shown in Table lll.

The asphalt employed in the compositions shown in Table lll was madefrom mixed Mid Continent and Wyoming crudes by steam and vacuumdistillation and tested as follows:

Penetration at 77F. 205 Softening Point (R&B), F. 102 Flash, COC, F. 620

Fire, COC, F. 710 Viscosity, SSF at 275F. 93 lnsolubles in CCl. Wt.%0.23 Oliensis Spot Test Negative Specific Gravity at 60F. 1.0002

The gas oil employed in the compositions shown in Table lll was made bydistillation of crude petroleum oil and tested as follows:

Gravity, APl 23.7 Flash, COC, F. 485 Fire, COC, F. 545 Viscosity,Kinematic at 210F. 12.54

The gas oil was composed primarily of saturated (paraffins andnaphthenes). This gas oil was analyzed by means of the standard clay-gelabsorption chromatographic method (ASTM D 2007-69) and was shown to havethe following composition:

Weight Saturates 54.2 Petroleum Resins 14.1 Aromatics 31.7

The foots oil employed in these compositions was prepared as previouslydescribed and had the properties and composition shown in Tables I andII.

Following their formulation, the compositions shown in Table lll wereairblown to produce the asphalt compositions shown in Table IV.

TABLE IV Air Blown Composition A B C D Penetration 1 3 i6 20 20Softening Point (R&B),F. 210 210 210 210 Barber Stain Value 1 3 4 1 Itmay be seen that the asphalt alone (composition A) when airblown to asoftening point suitable for laminating (210 F.) has an acceptableBarber Stain Test value but is much too low in penetration to beacceptable. The addition of 7 percent by weight of gas oil to theasphalt (composition B) resulted in a product acceptable in softeningpoint but having too high a stain test value and too low in penetration.The addition of 15 percent by weight of gas oil to the asphalt(composition C) resulted in a product acceptable in penetration andsoftening point but having too high a stain test value. Addition of only7 percent by weight of the foots oil of this invention to the asphalt(composition D), however, yielded an asphalt having completelysatisfactory softening point, penetration and stain test values forlaminating. These results are particularly surprising in view of thefact that both the gas oil and foots oil are composed primarily ofsaturated compounds (i.e., paraffins and naphthenes).

While this invention has been described with respect to various specificexamples and embodiments, it is to be understood that the invention isnot limited thereto and that it can be variously practiced within thescope of the following claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. An asphaltic composition which comprises an airblown mixture of atleast 50 percent by weight of an asphalt having a needle penetration at77 F. of about 150 to about 300 and a softening point (R B) of about F.to about 1 10 F. and between about 0.5 percent and about 20 percent byweight based on said asphaltic composition of a first pass foots oilfrom slack wax obtained from a waxy medium lube mineral oil distillateboiling primarily in the range of about 700 to l,000 F said foots oilcomprising about 40 50 weight percent nparaffins, about 5 to 15 weightpercent iso-paraffins, about 35 to 45 weight percent monocyclicnaphthenes and about 1 to 5 weight percent aromatics, and said asphalticcomposition having a softening point (R B) ofabout 185 F. to about 220F., a needle penetration of about 20 to S0 at 77 F. and a Barber StainValue in the range of from i to 2.

2. The composition of claim 1, which contains about 2.5 to about 10percent by weight of said foots oil.

3. The composition of claim 1, wherein said asphaltic composition has asoftening point of about 208"-2l2 F., and a needle penetration of about20-25.

4. The composition of claim 1, wherein said first pass foots oil has asoftening point of about F.

5. The composition of claim 4, wherein said first pass foots oil has asoftening point of about 100 F.

6. The composition of claim 1, wherein said composition has a BarberStain Value of l.

7. The composition of claim 3, wherein said composition has a BarberStain Value of l.

8. The composition of claim 5, wherein said composition has a BarberStain Value of l.

I l i I i

2. The composition of claim 1, which contains about 2.5 to about 10percent by weight of said foots oil.
 3. The composition of claim 1,wherein said asphaltic composition has a softening point of about208*-212* F., and a needle penetration of about 20-25.
 4. Thecomposition of claim 1, wherein said first pass foots oil has asoftening point of about 100* F.
 5. The composition of claim 4, whereinsaid first pass foots oil has a softening point of about 100* F.
 6. Thecomposition of claim 1, wherein said composition has a Barber StainValue of
 1. 7. The composition of claim 3, wherein said composition hasa Barber Stain Value of
 1. 8. The composition of claim 5, wherein saidcomposition has a Barber Stain Value of 1.